Exploitation of New Synthetic Reactions via Thermal Activation of Alkane C-H Bonds by Transition Metals

通过过渡金属热活化烷烃 C-H 键开发新的合成反应

• 批准号: 02453093
• 负责人: FUJIWARA Yuzo
• 金额: $ 3.71万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453093/
• 关键词: Alkane C-H Bond Activation; Palladium Catalysts; Cyclohexanecarboxylic Acid; Activation of Methane; Acetic Acid from Methane; Electrophilic Substitution; Copper Sulfate; Carbon Monoxide; 一酸化炭素; アルカンCーH結合活性化; 脂肪酸; 銅塩; モンサント酢酸プロセス; シクロアルカンのカルボキ

By studies on this project, the following novel useful synthetic reactions have been found and developed using alkanes as a starting material.1. Fatty Acid Synthesis from Alkanes and COWe found that the Pd (OAc)_2/K_2S_2O_8/CF_3COOH system catalyzes the carboxylation of alkanes with CO via thermal C-H bond activation. For example, cyclohexane reacts with CO (20 atm) to give cyclohexanecarboxylic acid in ca. 20000% yield (based on Pd). The reactions of cycloalkanes such as methyl-, t-butyl-, 1, 3-dimethyl-, trans-1, 4-dimethylcyclohexanes and adamantane with CO proceed regio- and stereo-selectively to give corresponding carboxylic acids. The reactivity of C-H bonds of cyclohexanes decreases in the order : tert->sec->primcarbon, and the stereochemistry of the substituents on the main products are all equatorial. By isotopic experiment, k_H/k_D=3 was obtained in the reaction of cyclohexane with CO. These results support that the reaction proceeds via electrophilic attack of Pd (II) to the C-H bond.2. Acetic Acid Synthesis from Methane with COUtilizing the above alkane activation reaction, acetic acid has been prepared in high yield from methane and CO. The catalysts are Pd (OAc)_2, Pd (O-COEt)_i or CuSO_4 and pressure of methane and CO is 20-40 atm, and reaction temperature is about 80ﾟC.Through this research project, alkanes such as methane have been found to act as good starting materials for organic synthesis.

通过对该项目的研究，发现并开发了以下以烷烃为起始原料的新型有用的合成反应。由烷烃和CoWE合成脂肪酸的研究发现，Pd(OAc)2/K2S2O8/CF3COOH体系通过热C-H键活化催化烷烃与CO的羧化反应。例如，环己烷与CO(20atm)反应生成环己烷羧酸，产率约为20000%(以Pd计)。甲基、叔丁基、1，3-二甲基、反式-1，4-二甲基环己烷、金刚烷等环烷烃与CO发生区域和立体选择性反应，生成相应的羧酸。环己烷的C-H键的反应活性按以下顺序递减：TERT-&GT；SEC-&GT；PRIMC，主要产物上取代基的立体化学都是赤道的。通过同位素实验，得到了环己烷与CO反应的kH/kD=3。这些结果支持反应是通过Pd(II)对C-H键的亲电攻击进行的。甲烷合成醋酸利用上述烷烃活化反应，甲烷和一氧化碳高产率地合成了醋酸。催化剂为Pd(OAc)2、Pd(O-CoEt)I或CuSO4，甲烷和CO的压力为20~40atm，反应温度约为80ﾟC。

项目成果

Koichi Satoh: "Pd-Catalyzed Regio- and Stereo-selective Carboxylation of cycloalkanes with CO" Chem. Lett.1433-1436 (1991)

Koichi Satoh：“Pd 催化环烷烃与 CO 的区域和立体选择性羧化” Chem。

Yuzo Fujiwara: "Look what Pd Catalyzes" Chemtech. 636-640 (1990)

Yuzo Fujiwara：“看看 Pd 催化什么” Chemtech。

Ken Takaki: "Alkane C-H Bond Activation" Kagaku (Chemistry). 46. 80-81 (1991)

Ken Takaki：“烷烃 C-H 键激活”Kagaku（化学）。

Tetsuro Jintoku: "Palladium Catalyzed Transformation of Benzene to Phenol with Molecular Oxygen" Chem.Lett.1687-1688 (1990)

Tetsuro Jintoku：“钯催化苯与分子氧转化为苯酚”Chem.Lett.1687-1688 (1990)

高木 謙: "アルカンのCーH結合活性化" 化学. 46. 80-81 (1991)

Ken Takagi：“烷烃的 C-H 键活化”化学 46. 80-81 (1991)。